Process for the manufacture of carbohydrate compounds



' Patented Oct. 4, 1938 UNITED STATES PATENT creme PROCESS FOR THE MANUFACTURE CAR- BOHYDRATE COMPOUNDS Wilhelm Neugebaner, Ulrich Ostwald, and Kurt Sponsel,

Wiesbaden-Biebrich, signors to Kalle & (lo.

Germany, as-

8 Claims.

In Germany 'Mareh 14, 1936 (Granted under the provisions ofaec. 14, act 0! Harch2,1927;3570.G.5)

a The present invention relates to processes for the manufacture of carbohydrate compounds.

It has been found that by causing carbohydrates in an alkaline medium toreact with olefine -sulfonic acids, particularly ,fiWtGd olefine sulfoni acids such as ethene sulfonlc acid, technically valuable carbohydrate others are obtained. Preferably large quantities of alkali are employed. In the reaction of cellulose with an olefine sulfonic acid, for instance, good results are obtained if so much alkali is employed that the cellulose and the employed sulfonic acid are present in the form of their alkali compounds. It is preferable to employ even more alkali because the reaction is favorably influenced by excess of alkali. The reaction takes place very readily. The process exhibits the advantage over other etheriflcation processes that no salts, the removal of which from the easily soluble reaction products would oflfer difliculties, are formed as by-products.

For the reaction, in particular high molecular carbohydrates such as cellulose, starch and the like, may be employed as may also substitution products thereof such as ether, mixed ethers and so forth, so long as they still contain in the molecule places capable of reacting. It.is further possible, after the conversion of the carbohydrates by the aid of the olefine sulphonates, to

subject the products obtained to still further conversions. Thus, for example, valuable products are obtained if cellulose is converted by the aid of an alkaline solution of sodium ethene sulphonate, and is treated after the termination of the reaction with still further alkylating means, such as methyl chloride, ethyl chloride, ethylene oxide, chloracetic acid and the like.

The quantity of the employed olefine sulphonic acids depends upon the desired properties of the products to be obtained. In general about 0.5-1-

molecule of olefine sulphonate is allowed to act on 1 molecule of cellulose (CsHmOs); Water soluble conversion products are-then obtained.

a If products soluble in alkali are desired then a 4 smaller quantity of olefine sulphonate sufilces.

The best reaction temperature in any given case is dependent on the alkali concentration employed. Thus, for example, in the -reaction of alkali cellulose with ethene sulphonate in the presence of 50% soda lye it is possible to work at 35-45 C., while when more dilute lyes are employed, higher temperatures are necessary, for example, when 30% lye' is employed, about (SO- C.

55 The products manufactured according to the invention can be employed as emulsifying andwashing means, particularly in admixture with moistening means, as thickening means, more particularly as thickening means for printing, as finishingandsizingmeansasprotectivecolloids 5 and for all pm'poses for which hitherto tragecanth and similar colloids were used.

u The following examples illustrate the invenon:

(1) kgs. of sm mte cellulose are soaked with 40% soda lye at room temperature. After standing for 12 hours the mass is pressed down to 260kgs.,isreducedtoflbersandismixedor kneaded respectively with 600 kgs. of a 50% soda lye. kgs. of finely ground sodium ethene sulphonate are then gradually worked in and the mixture is allowed to stand for a further 4 hours at 50 C., while kneading the mass, if desired. The reaction product yields with water a viscous solution. For the isolation of the sodium ceilulose-ethyl-ether-(fl) sulphonate, the procedure maybe adoptedthatthelyeclinsingtothere-' action product is pressed away from the latter, the pressed residue is mixed with water and is neutralized with hydrochloric acid. The cellulose ether is then precipitated out by treatment with a water soluble organic solvent such as methanol. The cellulose ether is then filtered, washed with 80% methanol, then dried:

(2)100 kgs. ofcellulose are soaked with .0% soda lye and pressed down to about 300 kgs. Esteriflcationisthencan'ledoutwith 10kgs.of ethylene oxide, for example, according to the mode of operation described in the German patent specification No. 536,993. The product thus produced is reduced to fibers and is mixed'o'r kneadedwith600kgs.ofa35% sodalye. Then 300 kgs. of a 50%aqueous solution of sodium ethene sulphonate are allowed gradually to run 40 inat 60 C. Themixtureisthenkeptatthe same temperature for a further 3-4 hours while stirring. When the resulting product is mixed with water a viscous solution is obtained, which,

even when rendered acid, does not separate out 45 in flocks. For theisolation of the reaction product, the mode of operation described in Example 1 8 -0fa50l6sodalyeand 55" isheateduptobo'c. Itisthenallowedtoremainatthistemperatm'eioraboutshours.

Thework'ingupoftheproductmsybeeflected inthemannerdescribedinmmplei.

'(4) 200gms.oisulphitecellulosearesoaked with2000gms.oia80%sodalyeat8C.and

'pressed down to about 2.6 times the original employed as thickening means, for example, for

vat dyes. It is possible to tree the product from impurities by washing it with 80% methanol or by slv s it- (5) 100 kgs. of methyl cellulose containing one methoxy group combined with two glucose units are soakedwith 600 kgs. of 45% soda lye. -Aiter three hours 180 kgs. o1 potassium ethene sulphonateareaddedwhilekneading. Themixmreis then heated up to 85' C. and allowed to remain 8-4 hours at this temperature. The obtained massisworkedupasdescribedinkxampiel.

We claim: LThemethodotetheflIyingacarbohydrs-te whichcomprisescausinganoleiinesulionicacidinanalkalinemediumtoreactwlththecarbohydrate. A

2. The method 01 etherifyins a carbohydrate which comprises causing an il-unsaturated oleiine sulionic acid in an alkaline medium to react with the carbohydrate.

3. The method of etherii'ying a carbohydrate which comprises causing ethene sulfonic acid in an alkaline medium to react with the carbohydrate.

4. The method oi! etherii'ying a substance selected from the group consisting of cellulose and its derivatives which comprises causing an oleilne sulionic acid in an alkaline medium to react with the said substance.

5. The method of etherlfying a substance selected from the group consisting of cellulose and its derivatives which comprises causing an 1.5- unsaturated oleilne suli'onic acid in an alkaline medium to react with the said substance.

8. The method of etherii'ying a substance selected irom the group consisting of cellulose and its derivatives which comprises causing ethene sulfonic acid in an alkaline medium to react with the said substance. 

